Phosphated mixed esters of oxyalkylated polyols and monohydric surface active compounds

ABSTRACT

At least partially water soluble phosphated mixed esters of nonsurface active polyols containing at least one hydroxyethyl group and monohydric surface active compounds containing oxyethylene groups are prepared by reacting said polyols and said monohydric compounds with polyphosphoric acid or phosphorus pentoxide at temperatures of 50*C. to 175*C. The products are useful as scale inhibitors in hard waters and are especially useful in squeezetype operation in oil recovery systems where the chemical must be adsorbed on the underground formation in such a manner that it is slowly released into the water as it passes over the formation.

United States Patent Stanford et al. [45] *Apr. 17, 1973 [5 PHOSPHATED MIXED ESTERS OF [56] References Cited ()XYALKYLATED POLYOLS AND UNlTED STATES PATENTS MONOHYDRIC SURFACE ACTIVE COMPOUNDS 3,502,587 3 1970 Stanford et al. ..252/l80 3,429,824 2/1969 Tate ..260/929 X 1 lnvemorsl James hlanford; Paul g 3,275,667 9/1966 Bohunek 8M1 ..260/929 x sang, Jr., bothof H s n, 3,056,744 10/1962 Copes etal. ..260/95l ux A 1 N 1 [73] ssignee la co Chemical Company Chicago Primary Examiner Lewls Gotts Assistant ExaminerAnton H. Sutto [*1 Notlcel The Portion of the mm of thls Attorney-Johnston, Root, O'Keeffe,-Keil, Thompson patent subsequent to Mar. 24, 1987, d sh nj ff has been disclaimed.

22 Filed: Dec. 9, 1969 [571 ABSTRACT App]. No.: 883,638

Related US. Application Data Division of Ser. No. 584,672, Oct. 6, 1966, Pat. No. 3,502,587.

Int. Cl. ..C07f 9/08, C02b [/18 Field of Search ..260/950, 929, 951

At least partially water soluble phosphated mixed esters of non-surface active polyols containing at least one hydroxyethyl group and monohydric surface active compounds containing oxyethylene groups are prepared by reacting said polyols and said monohydric compounds with polyphosphoric acid or phosphorus pentoxide at temperatures of 50C. to 175C. The products are useful as scale inhibitors in hard waters and are especially useful in squeeze-type operation in oil recovery systems where the chemical must be adsorbed on the underground formation in such a manner that it is slowly released into the water as it passes over the formation.

6 Claims, No Drawings 1 phosphated mixed esters of: (A) either oxyethylated or oxypropylated-terminally oxyethylated polyols, e.g.,

polyoxyethylated glycerol, ethylene glycol, hexylene glycol, sorbitol, mannitol or trimethylolpropane, or oxyethylated or oxypropylated-terminally oxyethylated erythritol, arabitol, xylitol, quercitol, inositol, and

mono-, di-, or tri-pentaerythritol and (B) oxyalkylated monohydroxy surface active compounds, e.g. oxyethylated nonyl phenol, oxyethylated tridecyl alcohol, and oxyethylated normal alcohol mixtures containing six or more carbon atoms.

The oxyalkylated polyols and surface active agents are phosphated by reaction with polyphosphoric acid or phosphorus pentoxide at elevated temperature, preferably in the order of about 50C. 175C. The reaction time is preferably at least about 30 minutes. The reaction may be conducted longer, however, e.g., up to 3-5 hours, to assure complete reaction. If desired, a catalyst such as BF etherate complex may be used. When using polyphosphoric acid the oxyalkylated polyol and the oxyalkylated surface active agent can be added to the polyphosphoric acid liquid. Conversely, the polyphosphoric acid can be added to a mixture of said oxyalkylated polyol and surface active agent.

The resultant reaction product may be used as is, or it may be converted to a salt by partial to complete neutralization with an alkaline substance such as, for

example, potassium or sodium hydroxide, potassium or sodium carbonate, ammonia, or a basic amino compound, e.g., tetramethyl ammonium hydroxide, methylamine, ethylamine, diethylamine, triethanolamine, diethanolamine, triethyl amine,

ethylene diamine, diethylene triamine, pyridine, morpholine or other amine. The amine should preferably be a water soluble amine or at least one that does not destroy solubility in water.

The polyols contain at least one, and preferably an average of at least about two, 2-hydroxyethyl groups (-CH CH OH) provided by the oxyethylation. The primary hydroxyl groups thereof are more effective than the secondary hydroxyl groups which would be provided by oxypropylation wherein R is a saturated, hydrocarbon radical having two to six carbon atoms,.R is a member selected from the group consisting of -CH CH and x is a number average in the range of O-5 inclusive, y is a number average in the range of l-6, inclu sive, preferably 3-5 and the sum of plus y equals 2-6, and z is a'number average in the range of 0-30, inclusive, and (B) a monohydric oxyalkylated surface active agent having a terminal 2-hydroxyethyl group, said phosphated compositions having an average of at least one and up to all of the hydroxyls of the 2-hydroxy ethyl groups and on an average of zero up to substantially all of said hydroxyl groups directly attached to th radical R replaced by phosphate ester groups derived from said phosphorus pentoxide, or polyphosphoric acid, said phosphate ester groups consisting essentially of one or both of a member selected from the group consisting of Also, the invention embraces the salts derived by the partial to complete neutralization of the phosphate ester groups.

Preferred embodiments include those in which said polyol is derived by oxyethylation of glycerol with 1.5

- to 2.5 mols of ethylene oxide per mol of glycerol; those in which said polyol is derived by the oxyethylation of mannitol with about 2-20 mols of ethylene oxide per mol of mannitol; those in which said polyols are derived by the oxyethylation of sorbitol with about 2-20'mols of ethylene oxide per mol of sorbitol; those in which said polyol is derived by the oxyethylation of trimethylolpropane with 1.5 to 2.5 mols of ethylene oxide per mol of trimethylolpropane; those in which said monohydric surface active agent is derived by the oxyethylation of alkyl phenols, e.g., containing four to 12 carbon atoms in the alkyl group or groups, preferably nonyl phenol or dinonyl phenol or mixtures thereof, or primary alcohols containing six to 18 carbon atoms, preferably tridecyl alcohol, or mixed six to 10 carbon atoms alcohols, with 2-20, preferably 4-14 moles of ethylene oxide per mole of such monohydric substance.

The invention further embraces a process for preventing hardness scale deposits on metal surfaces in contact with hard water containing hardness scaleforming ions which comprises contacting said metal surfaces with said hard water while maintaining therein a hardness-ion-precipitation-preventing quantity in the order of 0.5- parts per million of the previously described mixed esters and salts thereof.

The invention is particularly suitable for scale prevention by natural brines on ferrous metal walls and other surfaces in oil producing and water flood systems. Inorganic polyphosphates have long been the most effective and economical sequestering agents used for the prevention of alkaline deposits in both oil producing and water flood systems. However, due to the problems encountered in feeding inorganic polyphosphates and their incompatibility with many waters, a need for a liquid organic phosphate with good solubility in waters containing hardness ions has become increasingly evident. For this reason, a liquid product with good solubility in produced waters and having the effectiveness and low treating cost of inorganic polyphosphates is needed.

The invention has utility in the prevention of similar scale deposits occurring in closed and once-through cooling systems where hard water is employed.

The compounds may also have utility in boiler feed monomeric and some polymeric. Of course, some phosphate d oxyalkylated monohydric surface active agent can be present as well as some phosphated oxyalkylated polyol. While the phosphated surface active waters and inwaters charged to certain desalinization 5 agent alone Wlll have some scale inhibltor properties, equipment where scale deposition is a problem. h h h d 1k 1 d l l The invention may also be used in the prevention of t e p osp f y ate 90 yo w effectlve scale deposits in certain effluent and disposal waters, and combmatlon of the esPeclauy when particularly where other materials used in the prevenoxya kylated polyol and surface afmve tion of such deposits may constitute a pollution l agent are phosphated together, is better than either 1 component alone. problem. v

The following are examples of preferred embodithe foregomg E the Phosphauon w ments of the invention wherein the parts are by weight wlth polyphosphonf acid but It can be unless otherwise indicated phosphorus pentoxide. However, the reaction is smoother with polyphosphoric acid and is much easier EXAMPLE I to control. Glycerine and finely ground potassium hydroxide are Example? of further oxythylated polyhydnc coinpounds which can be obtained by the oxyalkylatlon charged mto an oxyalkylation reactor and are heated to o 2O procedure of Example I and can be phosphated as 150 C. while purging the reactor with natural gas. therein described are as follows Ethylene oxide is added slowly at l50l 60C. until the weight amount of added ethylene oxide equals the TABLEl weight of the glycerine. The reactor contents are recycled for an additional hour after all the ethylene oxide oxyalkylated Compounds is added to assure essentially complete oxyalkylation. A The weight of the added KOH was about 0.1 percent of d Eth I d the total weight of glycerine and ethylene oxide. Example figg z cmnpou" y em The phosphating procedure comprises charging 100 A, Glycerine (Ex. 1) 50.0 50.0 parts of the above polyoxyethylated glycerine, 50 parts 2: 5 5 33:; oxyethylated nonyl phenol (56.6 percent nonyl phenol A, Glycerine 25.0 and 44 4 ercent eth lene oxide) and 30 arts of 99 Femaerythmol P Y P A,, Glycerine 49.3 50.7 percent isopropanol, the latter as a viscosity control A, 35.0 65.0 agent, into a vessel free from moisture and oily or other 5 2;. Trimethylolpmpane 23: 3:2 foreign material. The charge is heated to C., Sorbitol 31.2

h 200 t f 1 h 11 'd l w ereupon par s 0 p0 yp osp onc am (a so Manniwl 705 295 called 115 percent phosphoric acid) is added in small A1: 50.0 50.0 amounts whereby the exothermic reaction is controlled 4 comp! by the rate of addition and by cooling to maintain a 0 temperature of -90C. When the polyphosphoric acid has been added, the temperature is allowed to in- Example S rfa Active Agent Ethylene Oxide 9 Name crease to the rangeof C. for about 30 m1r 1utes, B Nonyl phenol 5&6 A or less if the clarity of the reaction mass indicates 45 B, Nonyl phenol 40.0 60. complete reaction. 3: g P2 2%;

With the reactor on full cooling, 350 parts of tap 332 $1 1 water is added, slowly in the initial phase of water addi- B9 f y alcohol tion B, Higher alcohols 53.3 46.7

50 (butanol bottoms) The product is an aqueous solution of mixed esters 3 6-10 Carbon normal and mixtures of esters containing some monophosphate (MM 610) and some di-phosphate. Some of the esters are plus 01% ustic potash Parts oxy- Parts Parts Time, temp., After treatment, parts Exalkylated polyphosorganic ample compounds phoric solvent Hr. 0. H20 Caustic Alkano:

4 ml. BF:

3 100A ;100B 200 *50 0.5 90-95 400 0 0 4 10OAH50B2 200 *30 0.5 90-95 350 0 0 5 1009505019. 200 *30 0.5 90-95 350 0 0 1001195011; 300 30 0.5 90-95 450 o 0 1005050133 300 30 0.5 90-95 450 0 0 10%. 30133; 300 *30 0.5 90-95 450 0 0 9 100A! 30133 200 20 0.5 90-95 330 0 0 10 1005 20133 200 *20 0.5 90-95 320 0 0 11 100A1;10B1 200 *10 0.5 90-95 310 0 0 12 1OOA1;50B3 200 *30 0.5 90-95 40 15 0 505 100134 0 0.5 90-95 275 0 0 14 509.1;10013. 50 0 0.5 90-95 200 0 0 15 2051;100B1 100 *20 0.5 90-95 220 0 0 Parts oxy- Parts Parts Time, temp., After treatment, parts Exalkylatcd polyphosorganic ample compounds phorlc solvent Hr. C. H2O Caustic Alkanol 1001M; 40B; 200 '30 0. 5 90-95 340 0 100/i 100B; 400 30 (L5 90-95 340 0 0 100A]; 100B; 400 30 0.5 90-95 600 0 125 IUUAJ; 50B; 200 '30 0. 5 90-95 350 0 0 20. 100A]; 50B; 200 30, "30 0. 5 90%)5 350 0 0 21 100A;; 5013; 200 "30 0. 5 90-95 350 0 0 22.. 75A); 75Ba 200 "'0 0.5 90-95 350 0 0 23 75A1; 75135 200 30 0.5 90-95 350 0 0 150 *"50 0. 5 90-95 350 0 0 200 0 0. 5 90-95 350 0 0 200 "30 0. 5 90-95 375 0 0 200 30 0. 5 90-95 400 0 0 200 "30 0.5 90-95 350 0 0 29 75A1;100Ba 200 30 0.5 90-95 375 O 0 30 50A1; 100B; 200 "30 0. 5 90-95 350 0 0 31 A]; 100B; 200 0. 5 90-95 325 0 0 32 100.53; 100B; 150 0 0.5 90-95 200 0 0 33-. 100A;; 100133 150 0 0. 5 90-95 200 0 0 34 100.53; 10013 250 "30 0. 5 90-95 450 0 0 GOA]; 215Bo 170 0 0. 5 100 395 0 0 60A]; 215B@ 255 0 0. 5 100 480 0 1 50 60A]; 215B 340 0 0. 5 160 565 0 l 50 38 30A1; 215135 170 0 0.5 160 365 0 1 50 3' 30AM 215135 255 0 0. 5 100 450 0 1 50 40 30A1; 215Bq 340 0 0.5 100 535 0 1 50 41.- 120A]; 215B; 170 0 0. 5 100 455 0 1 50 42 120A 21585 255 0 0. 5 100 540 0 1 50 4 1201M; 216B:Y 340 0 0. 5 100 625 0 l 50 4 120111; 215B 425 0 0. 5 100 710 0 1 50 45 6014.1; 2153a 340 0 0. 5 100 565 0 1 46.. 30A1; 215136 170 0 0.5 100 365 0 50 47 90Ai; 320B5 340 0 0.5-1 100 700 O 50 48 45A1; 160B5 340 0 0. 5-1 100 495 0 1 50 49 120A]; 215135 425 O 1 90 1,060 0 l 50 =n-propanol. =n1ethanol. 99% isopropanol. Liquid 50% NaOH in water. 039% acetic acid. "hydroxy acetic acid. G=ethylone glycol.

EXAMPLE 50 catalyst. The ethylene oxide addition took about one This Example illustrates carrying out the process by adding the oxyalkylated polyol and oxyalkylatd surface active agent to warm liquid poiyphosphoric acid.

425 parts of poiyphosphoric acid was placed in a three neck reaction flask provided with agitation and heating means. THe temperature was raised to C. and a mixture of the following, heated to 50C., was slowly added:

215 parts B 120 parts A,

The addition rate was regulated so that the temperature of the reaction mass increased to 130C. When the addition was finished, the reaction mass was held at 130C. for 30 minutes. it was then cooled to C., 50 parts of n-propanol was added, followed by cooling to 60C., the addition of 50 parts methanol, agitation for l0 minutes and the addition of 1060 parts water.

EXAMPLE 51 In a reaction vessel equipped with a stirrer, parts of the oxyalkylated glycerine A 200 parts of oxyethylated high boiling alcohols and 90 parts of P 0 are heated and reacted at 185190C. The reaction mixture is refluxed for 15 minutes. After cooling, the reaction production is diluted with 390 parts of water and is neutralized with caustic soda flakes.

The specific mixture in this example was a heavy alcohol mixture called butanol bottoms" and comprised n-butanol, 3 percent; C alcohols, 0.5 percent; C alcohols, 10 percent; C alcohols, 23 percent; C alcohols, 45 percent; and C,,C alcohols, 14 percent. The alcohols were mostly primary, branch chain alkanols. They were oxyethylated at -l60C. with 345 parts by weight of ethylene oxide per parts of the heavy alcohol mixture with 0.1 percent by weight of finely ground potassium hydroxide as the alkaline hour at 120-160C. and was followed by a one hour recycle period of C.

Example 51 illustrates the use of P 0 as the phosphating agent.

Lower alkanols, particularly n-propanol or isopropanol, may be present in the phosphating reaction as viscosity control agents. Other solvents can be used, e.g., dioxane and toluene. Lower alkanol phosphates which form by the reaction of the alkanol and the phosphating agent are not particularly active as scale inhibitors.

On the other hand, phosphated esters and/or salts thereof of oxyethylated higher alkanols having at least 4 carbons, preferably six to 20 carbon atoms, are used in the invention is admixture with, or as mixed esters with, the phosphated esters of oxyalkylated polyols. The oxyethylated alkanols contain about 2-20 mols of oxyethylene groups per mol of alkanol and have the general formula wherein R is a straight chain or branch chain alkyl group of at least 4 and preferably at least six carbons. Mixture of two or more alkanols are also contemplated by the invention. Other higher molecular weight oxyalkylated surface active substances containing primary hydroxyl groups which can be phosphated wtih poiyphosphoric acid or P 0 e.g., the oxyethylated alkyl phenols, provide compositions in the form of mixed phosphate esters or mixtures of esters which are very useful.

In preparing these compositions, the weight ratio of oxyalkylated polyol to oxyalkylated monohydric surfactant containing a Z-hydroxyethyl group is preferably within the range of 1:10 to 10:1.

The compositions of the invention are especially effective in the inhibition of scaling on metal surfaces by calcium sulfate, barium sulfate, and calcium carbonate. They are useful in the oil production industry to prevent deposits of these scale-producing compounds on metal surfaces of pumps, pipes, valves, tanks, and the like when waters containing the scale-producing compounds (or precursors thereof, e.g., calcium bicarbonate) are treated in the concentrations aforesaid, i.e., 0.5 to 100 parts per million. Places where scale build up is most likely to become troublesome are those in the liquid handling systems wherein there is a change in fluid pressure, a change in fluid temperature, or a change in fluid flow rate.

The invention may be used in waterflood systems used to inject water into subterranean formations, wherein the water is brackish or is a brine conducive to scale formation on metal surfaces of the waterflood system. Typical brines encountered in waterflood operations, wherein water is drawn from sources available at or near the waterflood site, are:

Brine A Brine B Chloride (NaCl) 49,000 mg/l. 28,000 mg/l. Total Hardness (CaCO 5,300 mg/l. 3,400 mg/l. Calcium (CaCO,) 4,900 mg/l. 1,600 mg/l. Alkalinity P(CaCO;,) 120 mg/l. 80 mg/l. Alkalinity M(CaC:,) 1,050 mg/l. 130 mg/l. Sulfate (NaSO 0 4,750 mg/l. pH 7.8 8.3

Any of the products previously described can be used to prevent scale formation on metal walls of pipes, pumping equipment and storage tanks used to inject flood waters into subterranean formations. The dosage will vary depending on the particular composition and the type of brine in the formation but, in general, effective control is obtained with to 20 parts per million (ppm) of inhibitor and in some cases as low as 0.5 ppm is effective. Thus, the inhibitor of Example 49 is effective in inhibiting scale by brines A and B at 10-20 ppm.

in cooling waters of closed cooling systems, wherein the cooling water is a typical municipal tap water, maintenance of dosage levels of -30 ppm. are typical, although higher levels up to about 100 ppm. may be needed or desired in particular cases.

In low pressure boilers, dosage levels in the range of 50-250 ppm. may be employed in the feed water, a typical level being about 80-100 ppm. I

The compositions of the invention are useful in a number of areas where scaling of metal surfaces, particularly ferrous metal surfaces, by barium sulfate, calcium sulfate and/or calcium carbonate is a problem. By control of scale formation, breakdowns, maintenance, cleaning and repairs caused or necessitated by scale formations can be minimized.

ln comparative tests using brines'made by dissolving 7.5 grams of sodium chloride and 8.33 grams of calcium chloride in distilled water sufficient to make I liter (Brine C) and 7.5 grams sodium chloride plus 1066 grams Na SO in distilled water sufficient to make 1 liter (Brine D), it was found that the composition of Example l was partially effective in preventing calcium sulfate deposition at 1 ppm. and completely effective at 2 ppm. when 50 ml. of each brine were mixed and heated for hrs., at 160F. A control test with no additive gave a deposit of l 350 ppm. CaSO calculated as CaCO The composition of Example 44 gave no deposits at l ppm. added to 100 ml. of the brines C and D. At the same dosage a phosphated oxyethylated glycerinc without the oxyethylated tridecyl alcohol component gave a deposit of 400 ppm. CaSO,, calculated as CaCO thereby indicating that the mixed ester is more effective than the phosphated oxyethylated polyol alone.

Calcium carbonate deposition tests also indicated a superiority for the compositions of the invention. Thus, the compositions of Examples 44, 47 and 48 prevented calcium carbonate deposition on the surface of test cells containing 20 ml. of brine (Brine E) made by dissolving 8.4 grams of NaHCO in one liter of distilled water, ml. of brine (Brine F) made by dissolving l 1.1 grams of CaCl in 1 liter of distilled water and 90 ml. of brine (Brine G) which was a 10 percent solution of sodium chloride in water, mixed together and heated for 20 hours at l60F. Complete inhibition of calcium carbonate deposition was obtained with all three compositions at dosages of 5 ppm., 10 ppm. and 30 ppm. and with Example 44 at 3 ppm. The blank control deposited 380 ppm. A phosphated polyol was completely effective at a dosage of 10 ppm. and 30 ppm. but only partially effective at 3 ppm. and 5 ppm.

The process of the invention can be carried out with relative ease and is especially important where the polyols have closely spaced hydroxyls such as glycerine and pentaerythritol. The addition of 2-hydroxyethyl groups spaces the hydroxyl groups and makes it easier to produce phosphate esters without forming a viscous mass. The final products are preferably acidic, e.g., pH 4.5-6, because water solubility decreases and solids precipitate at pl-ls above 7.

In the process for making phosphate esters previously described it will be understood that where a solvent is used the process is carried out at a temperature below the boiling point of the solvent.

The solvents used act as combination solvents and viscosity control agents, although any solvents, e.g., hydroxyacetic acid, having a reactive hydroxyl group will react in the phosphation and influence the overall composition of the final product.

It will also be understood that other surface active agents can be used provided they contain a 2-hydroxyethyl group. Numerous examples are given in Mc- Cutcheons Detergents and Emulsifiers" 1966 Annual.

In a number of oil fields in West Texas and other areas, water floods have been established in which waters incompatible with the connate waters were used for injection. This occurs when a good source of compatible water is not available. Most of these floods are using a high sulfate water to flood a formation which has a high calcium content water. As the'waters reach the producing well they mix, and a calcium sulfate deposition occurs, either in the formation at the well bore or in the producing equipment. This requires the removal of the tubing, rods and pump for cleaning,and a fracturing job if the formation is plugged, which is the case most of the time. By the practice of the present invention the formation of scale in the producing equipment and underground formation can be reduced or prevented. However, as the scale forms in the producing formation, the scale control chemical must be squeezed into the producing underground formation so it can be produced back slowly in one of the waters before they mix. To give long term scale inhibition the chemical must be adsorbed on the underground formation in such a manner that it is slowly released into the water as it passes over the formation so that a chemical concentration of one to 10,000 ppm. is always in the water. Some scale control compounds when squeezed into the formation are so tightly adsorbed that little, if any, feedback occurs, while others are essentially not adsorbed and feedback occurs immediately with no extended protection given. The chemicals of the present invention have unique adsorption-desorption properties in that they are adsorbed on solid surfaces and slowly released into the produced water or brine over a period of time to give long term protection against scale deposition in the surfaces of the formation face and the producing equipment.

In a typical application, five to ten barrels of water from a producing oil well are pumped into an oil well. A chemical composition as herein described is then in- 10 agent being from the group consisting of (a) oxyethylated alkyl phenols and mixtures thereof containing 4 to 12 carbon atoms in an alkyl group oxyethylated with -2 to moles of ethylene oxide per mole of said alkyl phenol and .(b) oxyethylated alkanols and mixtures thereof having the general formula wherein is a straight chain or branch chain alkyl group having at least four carbon atoms, said phosphate mixed ester having an average of at least one and up to all of the hydroxyls of the 2-hydroxy ethyl groups and on an average of zero up to substantially of jected into the well and displaced or squeezed" I through the underground oil-bearing formation by pumping 50 to 150 barrels of produced water into the well, depending upon the amount of water being produced. The produced oil and water are then pumped from the well.

Similarly, the invention is applicable to the treatment of water supply wells. The pre-addition of water to the well can be omitted. The phosphate mixed esters or mixture of esters can also be added directly to the input well of a waterflood system consisting of one or more input wells and one or more producing wells.

The invention is hereby claimed as follows:

1. A phosphate mixed ester of: (A) a polyol of the formula wherein R is a saturated, hydrocarbon radical having two to six carbon atoms, R is a member selected from the group consisting of x is a number average in the range of 0-5, inclusive, y is a number average in the range of 1-6, inclusive, and the sum of x plus equals 2-6, and z is a number average in the range of 0-30, inclusive, and (B) a monohydric oxyalkylated surface active agent having a 2-hydroxyethyl group, said monohydric surface active said hydroxyl groups directly attached to the radical R replaced by phosphate ester groups, said phosphate ester groups consisting essentially'of one or both of a member selected from the group consisting of the weight ratio of (A) to (B) being within the range of 1:10 to 10:1.

2. A water soluble salt derived by the partial to complete neutralization of said phosphate ester groups of a composition as claimed in claim 1.

3. A phosphate mixed ester as claimed in claim 1 wherein said polyol is derived by oxyethylation of glycerol with 1.5 to 2.5 mols of ethylene oxide per mol of glycerol.

4. A phosphate mixed ester as claimed in claim 1 wherein said surface active agent is an oxyethylated alkyl phenol containing 4-12 carbon atoms in an alkyl group oxyethylated with about 2-20 mols of ethylene oxide per mol of said alkyl phenol.

5. A phosphate mixed ester as claimed in-claim 1 wherein said surface active agent is derived by oxyethylation of tridecyl alcohol with about 2-20 mols of ethylene oxide per mol of tridecyl alcohol.

6. A phosphate mixed ester as claimed in.claim 1 wherein said surface active agent is an oxyethylated mixture of six to 10 carbon atom primary alcohols. 

2. A water soluble salt derived by the partial to complete neutralization of said phosphate ester groups of a composition as claimed in claim
 1. 3. A phosphate mixed ester as claimed in claim 1 wherein said polyol is derived by oxyethylation of glycerol with 1.5 to 2.5 mols of ethylene oxide per mol of glycerol.
 4. A phosphate mixed ester as claimed in claim 1 wherein said surface active agent is an oxyethylated alkyl phenol containing 4-12 carbon atoms in an alkyl group oxyethylated with about 2-20 mols of ethylene oxide per mol of said alkyl phenol.
 5. A phosphate mixed ester as claimed in claim 1 wherein said surface active agent Is derived by oxyethylation of tridecyl alcohol with about 2-20 mols of ethylene oxide per mol of tridecyl alcohol.
 6. A phosphate mixed ester as claimed in claim 1 wherein said surface active agent is an oxyethylated mixture of six to 10 carbon atom primary alcohols. 